High productivity bisphenol-a-catalyst

ABSTRACT

A high productivity catalyst for bisphenol-A has been discovered which comprises strongly acidic cation-exchange resin spheres produced from a polystyrene/divinylbenzene (PS/DVB) copolymer sulfonated under conditions to introduce sulfone cross-linking. Surprisingly, the sulfone cross-linking improves the resistance to deformation but does not have a negative effect on the activity and selectivity of the catalyst in bisphenol-A production.

[0001] The present invention relates to a catalyst composition forsignificantly increasing the productivity of fixed-bed reactors in theproduction of bisphenol-A.

[0002] Industrial production of bisphenol-A (BPA) currently involves aprocess whereby a mixture of excess phenol and acetone is passed througha cylindrical fixed-bed reactor filled with divinyl benzene cross-linkedsulfonated polystyrene ion exchange resin catalyst. The direction offlow of the mixture may be either downwards or upwards as required byreactor design. Each feed direction has its own advantages anddisadvantages. Typically, the flow of the viscous reactant mixture isdown-flow. Where the feed directions is downwards, the pressure dropthrough the sulfonic acid resin catalyst bed is a major problem limitingthe throughput of reactants and products, which ultimately limits theproduction of bisphenol-A. The pressure drop is caused by a variety offactors, including the viscosity and density of both reactants andproducts, particle size and particle size distribution of catalyst andthe compressibility of the catalyst. The compressibility of the sulfonicacid catalyst appears to be an important factor relating to the pressuredrop level. The spherical catalyst particles can be compressed/deformedunder pressure into a variety of non-spherical or lenticular shapes anda loss in bed void fraction, leading to an exponential reduction inthroughput. Moreover, compression of the catalyst bed under pressure canpromote the formation of flow channels so that flow through the reactoris not uniform. As a result, the quantity of catalyst used as a wholemay not be fully utilized.

[0003] An optimized catalyst system for the synthesis of bisphenol-A hasbeen disclosed by Berg et. al. in U.S. Pat. No. 5,395,857. Berg et. al.disclose sulfonic acid catalyst beds for increasing the volume/timeyield of fixed-bed reactors in the production of bisphenol-A from phenoland acetone in cylindrical fixed-bed reactors filled with gel-form ormacroporous sulfonic acid ion exchange resin catalysts, characterized inthat the lower layer of the bed consists of a resin having a low degreeof cross-linking (<2%) and makes up 75 to 85% by volume of the bed as awhole and the upper layer of the bed, which makes up 15 to 25% byvolume, consisting either of a resin having a higher degree ofcross-linking (≧2% to ≦4%), in which 1 to 25 mole % of the sulfonic acidgroups may be covered with species containing alkyl-SH units (ionicfixing) or of a resin having a low degree of cross-linking (<2%), inwhich 1 to 25 mole % of the sulfonic acid groups are covered withspecies containing alkyl-SH units (ionic fixing).

[0004] Yet another catalyst system for the synthesis of bisphenol-A hasbeen disclosed by Kissinger et al. in the International Publication No.WO 00/50372A1. Kissinger et al. discloses an improved process for theproduction of bisphenol-A employing a catalytic ion exchange resin bedin which the lower portion of the bed is filled with a resin which has ahigher degree of crosslinking than the upper layer and the upper portionof the bed is filled with an unmodified resin having a low degree ofcrosslinking or a resin having a low degree of crosslinking in which 1to 35 mol % of the sulfonic acid groups are covered with speciescontaining alkyl-SH groups by ionic fixing.

[0005] A reactor system for bisphenol-A is also disclosed inInternational Publication No. WO 97/34688 in which the reactor isoperated in an upflow mode with a fixed bed catalyst and randomlydistributed reactor packing, employing lightly cross-linked ion exchangeresin catalysts, typically containing no greater than 2 to 4 %divinylbenzene cross-linking.

[0006] It is preferred that in both reactor systems, the catalysts aresulfonated aromatic resins comprising cross-linked polymers, typicallypolystyrene/divinyl benzene (PS/DVB) copolymers, having a plurality ofpendant sulfonic acid groups. In both types of reactor systems, when thecatalyst contains 1 to 3% cross-linking, catalyst compression and theresulting pressure drop becomes more limiting than the acetone reactionrate. The compressibility of the catalyst particles can be decreased byincreasing the amount of cross-linking material (divinyl benzene) usedin the copolymerization. However, as taught in U.S. Pat. No. 5,395,857,increasing the amount of cross-linking material decreases the reactivityand selectivity of the bisphenol-A catalyst to produce BPA.

[0007] A process has been discovered in which the pressure drop in theindustrial production of bisphenol-A from acetone and phenol in acylindrical fixed-bed reactor filled with sulfonic acid ion exchangeresin catalysts in large quantities can be significantly reduced.According to the present invention, catalyst compressibility can besubstantially decreased by cross-linking the PS/DVB copolymer withsulfone bridges during the sulfonation process. Surprisingly, thesulfone cross-linking does not have a negative effect on the activityand selectivity of the catalyst in bisphenol-A production. Thesulfonation process used to introduce sulfone cross-linking has alsobeen found to introduce additional sulfonic acid groups so that theaverage styrene aromatic ring contains more than one sulfonic acidgroup. The catalysts used in the process of the present inventionprovide an unexpected combination of desired performance properties inthe synthesis of bisphenol A: reactivity, selectivity, compressibilityand hydraulic characteristics.

[0008] According to present invention, a high productivity catalyst forbisphenol-A has been discovered which comprises strongly acidiccation-exchange resin spheres produced from a polystyrene/divinylbenzene(PS/DVB) copolymer sulfonated under conditions to introduce sulfonecross-linking. Surprisingly, the sulfone cross-linking improves theresistance to deformation but does not have a negative effect on theactivity and selectivity of the catalyst in bisphenol-A production. Thecatalysts used in the process of the present invention provide anunexpected combination of desired performance properties in thesynthesis of bisphenol A: reactivity, selectivity, compressibility andhydraulic The bisphenol-A catalyst of the present invention ischaracterized in that the spherical catalyst particles substantiallyresist deformation under pressure as compared to currently knownbisphenol-A catalysts and posses higher reactivity as compared tocurrently known bisphenol-A catalysts.

[0009] According to present invention, a high productivity catalyst forbisphenol-A has been discovered which comprises strongly acidiccation-exchange resin spheres produced from a polystyrene/divinylbenzene (PS/DVB) copolymer sulfonated under conditions to introducesulfone cross-linking.

[0010] The spherical bisphenol-A catalyst particles were formed bysuspending a mixture of styrene and divinyl benzene monomers andinitiators in an aqueous liquid, and subsequently polymerizing themixture to produce spherical copolymer beads, that when sulfonated tointroduce sulfonic acid groups and sulfone cross-linking give a catalystof surprisingly high reaction rates when used to catalyze the conversionof phenol and acetone to bisphenol-A.

[0011] The process by which the catalyst is made, comprises suspending amixture of styrene and divinyl benzene monomers and a free-radicalpolymerization initiator into an aqueous suspending medium that isagitated to form monomer droplets, heating the droplets to a temperatureabove the activation temperature of the polymerization initiator untilthe droplets polymerize, separating the resulting polymer beads from thesuspending medium, drying the beads, functionalizing the beads withstrongly acidic cation-exchange groups and sulfone cross-links. Theprocess of making such types of ion exchange resin catalysts of uniformparticle size without sulfone cross-linking is disclosed by Lundquist inU.S. Pat. No. 5,233,096.

[0012] The styrenic monomers useful in preparing the cross-linkedcopolymer beads of the present invention include styrene and substitutedstyrenes such as α-methyl styrene, vinyltoluene, ethyl vinyl benzene,vinyl naphthalene and the like. The cross-linking monomers containing aplurality of ethylenically unsaturated functional groups includearomatic cross-linking monomers such as divinyl benzene, divinyltoluene, trivinyl benzene, divinyl chloro benzene, diallyl phthalate,divinyl naphthalene, divinyl xylene, divinyl ethyl benzene, trivinylnaphthalene and polyvinyl anthracenes; and aliphatic cross-linkingmonomers such as di- and polyacrylates and methacrylates exemplified bytrimethylolpropane trimethacrylate, ethylene glycol dimethacrylate,ethylene glycol diacrylate, neopentyl glycol dimethacrylate andpentaerythritol tetra- and trimethacrylates, and trivinyl cyclohexane.The cross-linking monomer is preferably present at levels from about0.1% to about 20 weight percent of the total monomer, and morepreferably from about 1% to about 10 weight percent of the totalmonomer. Preferred cross-linking monomers are aromatic cross-linkingmonomers, and particularly preferred is divinyl benzene.

[0013] The jetting suspension-polymerization process useful for formingthe uniform cross-linked copolymer beads of the present invention isexemplified by, but not limited to, the process disclosed by Koestler etal. in U.S. Pat. No. 3,922,255. In that process, a minimal solubility ofthe monomers in the aqueous suspending medium is important. Solubilitycan be decreased by adding an electrolyte to the aqueous suspendingmedium. The jetting process produces monomer droplets in the suspendingmedium whose average diameter for the droplet population is preferablyvaried over the range from about 20 μm to about 1 mm, and the resultingcopolymer beads may be produced with an average diameter for the beadpopulation which varies over the same range. The jettingsuspension-polymerization process produces a droplet size distributionthat is narrow, resulting in uniformly sized droplets and uniformlysized copolymer beads. Other processes which form uniformly sizedcopolymer beads by jetting monomer into an aqueous suspending liquid maybe used, as for example that disclosed by Timm et al. in U.S. Pat. No.4,623,706, which uses a vibrating orifice to jet the monomer into thesuspending medium. The suspending medium preferably moves with relationto the jetting orifice or orifices, and the monomer droplets may eitherby polymerized in the vicinity of the orifices by jetting the monomerinto the suspending medium at the polymerization temperature, or theymay be polymerized in a different zone of the polymerization apparatusby causing the moving suspending medium to carrying them into a heatedpolymerization zone. Alternatively, the uniform jetted monomer beads maybe encapsulated with stable shells and polymerized as taught by Lange etal. in U.S. Pat. No. 4,427,794.

[0014] The polymerized beads may be separated from the suspension mediumby gravity, by centrifugal flow, by hydraulic separation or byfiltration.

[0015] The monomers may be jetted by themselves, or mixed with inertliquids or prepolymers which are dissolved in the monomers or formed byprepolymerization of the monomers, or by a combination of both methods.The preferred jetting rate produces a ratio of suspending medium tomonomer of from about 1.5:1 to about 10:1, and more preferably fromabout 2:1 to about 5:1. The monomer may be jetted into the suspendingmedium at a temperature about the activation temperature of thefree-radical polymerization initiator described below, which will causepolymerization to begin almost immediately, or the medium may be belowthe activation temperature, but preferably above about 15° C., and beheated subsequently, after flowing into a heating zone; this will permitthe monomer droplets to stabilize before polymerization begins.

[0016] All commonly used stabilizers, especially gelatin, starch,carboxymethylcellulose, polyacrylic acids, polyvinyl alcohol; orwater-insoluble inorganic stabilizers in particulate form, such asbentonite, magnesium hydroxide and the like; or combinations of suchstabilizers may be used to stabilize the monomer droplets in this orother jetting suspension-polymerization processes.

[0017] Free-radical polymerization initiators are preferred to initiatepolymerization of the monomer droplets suspended in the suspendingmedium. Preferred free-radical polymerization initiators are oil-solubleinitiators which are dissolved in the monomer, such as benzoyl peroxide,lauroyl peroxide, t-butyl peroctoate, t-butyl peroxy benzoate, t-butylperoxy pivalate, t-butylperoxy-2-ethylhexanoate, bis(4-t-butylcyclohexyl)peroxy dicarbonate and the like; and azo compounds such asazo bis(isobutrylonitrile), azo bis(dimethyl valeronitrile) and thelike. The polymerization temperature, that is, the temperature at whichthe suspending medium is held during polymerization of the monomerdroplets, and the polymerization initiator are interdependent in thatthe temperature must be high enough to break the chosen initiator downin to an adequate number of free radicals to initiate and sustainpolymerization, that is, it must be above the activation temperature ofthe initiator. Preferred polymerization temperatures are from about 40°C. to about 100° C., and more preferably from about 50° C. to about 90°C., and the free-radical initiator is chosen so that it has anactivation temperature below the polymerization temperature.

[0018] According to the present invention, spherical particles of thebisphenol-A catalyst were obtained by sulfonating a styrene/divinylbenzene copolymer under conditions to introduce sulfonic acid groups andsulfone cross-linking. Surprisingly, the sulfone cross-linking preventsbead deformation and yet does not have a negative effect on the activityand selectivity of the catalyst in bisphenol-A production. Morespecifically, the catalyst resins of the present invention involvestrong acid, sulfone cross-linked PS/DVB ion exchange resins having arelatively low degree of divinyl benzene cross-linking, from 0.5 % to4.5 %. In a preferred embodiment, the invention is directed to uniformlysized beads of a strong acid, sulfone cross-linked PS/DVB ion exchangeresin catalysts produced by the cross-linking and functionalization of aspherical PS/DVB copolymer bead of uniform size.

[0019] According to the present invention, a novel class of sulfonecross-linked PS/DVB ion exchange resin catalysts having excellentphysical stability and high capacity for conversion of phenol andacetone to bisphenol-A. The resins are produced by a novel route whichbegins with a polymer bead, preferably of uniform size, avoiding therequirement for later separation of off-size particles. By the method ofthe invention, linear PS, DVB and PS/DVB copolymers may be both sulfonecross-linked and finctionalized simultaneously with the sulfonatingreagent mixture to afford catalysts of the present invention. Sulfonecross-linked polystyrene materials and the process to produce suchmaterials are disclosed by Amick in U.S. Pat. No. 4,177,331. The processdescribed in U.S. Pat. No. 4,177,331 produced a sulfone cross-linkedlinear polystyrene resin that had excellent physical stability and highcapacity for ion exchange. A method for producing sulfone cross-linkedmaterials from seeded, cross-linked polystyrene copolymers is disclosedby Harris, et. al. in U.S. Pat. No. 5,616,622. The oxidative stabilityof seeded cation exchange resins could be increased by the introductionof secondary cross-linking such as sulfone cross-links.

[0020] Sulfonation of PS/DVB by the process of the present inventionaccomplishes not only sulfone cross-linking of the polymer but yieldscatalysts containing polysulfonation in which the aromatic ring containsmore than one sulfonic acid group per ring. Sulfonated cross-linkedvinyl benzene polymers containing more than one sulfonic acid group peraromatic nucleus and a process of producing such sulfonated polymers aredisclosed by Corte et. al. in U.S. Pat. No. 3,158,583.

[0021] It was found that granules or beads of PS/DVB copolymer may besulfone cross-linked and functionalized with a particular sulfonatingreagent mixture in an efficient and controllable manner. The reagentsuseful by the process of the invention include various combinations ofchlorosulfonic acid, sulfur trioxide, sulfuric acid, and boron compoundsuch as boric acid and boron oxide. The combinations of sulfonatingreagents and boron compounds most desirable for introducing sulfonecross-linking to cross-linking PS/DVB copolymers are as follows:sulfuric acid/sulfur trioxide, chlorosulfonic acid/sulfur trioxide,chlorosulfonic-sulfur trioxide/boron compound, chlorosulfonicacid/sulfuric acid/boron compound, sulfur-trioxide/sulfuric acid/boroncompound.

[0022] The sulfonation of aromatic compounds, either monomeric orpolymeric, taught heretofore with chlorosulfonic acid or sulfur trioxideinherently lead to the formation of some sulfone linkages It is knownthat sulfone bridges result from the electrophilic attack of“pyrosulfonic acid” intermediates upon unreacted aromatic rings; theseintermediates are, in turn, formed by the reaction of a sulfonic acidwith SO₃ (W. H. C. Ruegeberg, T. W. Sauls, and S. L. Norwood, J. Org.Chem., 20, 455, 1955). We have found that by adjusting the concentrationof the sulfuric acid /SO₃ mixture, that the number of sulfone bridgescan be controlled. It is preferred that sulfuric acid/SO₃ mixtures, alsoknown as oleum, having acid concentrations of between 101.0% and 104.5%(20% oleum contains 20% by weight of SO₃ in 100% sulfuric acid, for afinal acid concentration of 104.5%) be used as the sulfonating agents tointroduce both sulfone bridging groups and at least one sulfonic acidgroup per aromatic nucleus.

[0023] The number of sulfone bridges contained in the catalyst of thepresent invention can be determined by subtracting the mmol of sulfonicacid groups per gram of dry catalyst, determined by titration of thesulfonic acid groups, from the mmol of total sulfur determined byelemental analysis. The difference is the mmol of sulfone bridges pergram of dry catalyst. In theory, if each of the aromatic rings issulfonated, the low cross-linked cation exchange resin should have acapacity of 5.1 mmol acid groups per gram of dry resin and an elementalanalysis of sulfur of 16.2 weight percent. If a catalyst was found tohave a capacity of 5.7 mmol acid groups per gram of dry catalyst and asulfur elemental analysis of 19%, then in one gram of dry catalyst 0.6mmol of the aromatic rings have two sulfonic acid groups and thecatalyst has 0.2 mmol of sulfone bridging groups.

[0024] The catalyst according to the present invention for the synthesisof bisphenol A represents an unexpected combination of reactivity,selectivity, compressibility and hydraulic performance for the synthesisof bisphenol-A. A preferred catalyst of the present invention comprisesa copolymer of between 1.0 and 6.0% divinylbenzene cross-linking,preferably between 1 and 4% divinylbenzene crosslinking, sulfonated to adry weight capacity of greater than 4.0 mmol/g and preferably greaterthan 5.1 mmol/g, possessing 0.1 to 1.0 mmol/g of sulfone bridginggroups.

[0025] The reactions catalyzed by the sulfone-bridged, strongly acidiccation-exchange resin beads of the present invention are those reactionsthat are catalyzed by the presence of strong acids, and include, but arenot limited to, condensation reactions, for example the condensation ofphenols with ketones or aldehydes to produce bisphenols. A preferredreaction which is catalyzed by the strongly acidic ion-exchange resinbeads of the present invention is the reaction of phenol with acetone.More preferred is that reaction in which phenol and acetone are combinedin a molar ratio of from about 20:1 to about 2:1 and the combination iscontacted, at from about 40° C. to about 100° C., with from about 1 toabout 40 weight percent (based on the weight of phenol and acetone) ofthe strongly acidic ion-exchange resin beads of the present invention,optionally in the presence of from about 0.1 to about 40 weight percent(based on the weight of phenol and acetone) of a mercaptan reactionpromoter, preferably ethanethiol, 3-mercaptopropionic acid, amino ethanethiol or dimethyl thiazolidine. Aminothiol promoters such as aminoethanethiol and dimethyl thiazolidine can be ionically attached to the ionexchange resin of the present invention. The attachment of ionicpromoters is described in U.S. Pat. No. 3,394,089.

[0026] Due to the size of fixed bed BPA reactors and the viscosity ofthe BPA reaction stream, BPA production rates are greatly affected bypressure drop. As such, catalyst factors such as particle size, particleuniformity and compressibility need to be understood in order to produceBPA at acceptable rates and allow for instantaneous production increasesto meet market demand. The particle size and uniformity of the BPAcatalysts can be tightly controlled as disclosed by Lundquist in in U.S.Pat. No. 5,233,096. The compression of the BPA catalyst bead is not wellunderstood but can be tested by measuring the deformation of thecatalyst bead under a gradual increase in force. The resultingmeasurement known as the compression modulus of the catalyst wasdetermined in a phenol swollen state using a Chatillion instrument withthe compression modulus being the slope of the line measuring theinitial deformation of the bead up to a force of 200 grams/bead.

[0027] The use of the strongly acidic cation exchange resin beadscontaining sulfone cross-linking for the condensation of phenols withaldehydes or ketones allows for higher production rates of BPA byincreasing both catalytic and hydraulic performance. The increasedhydraulic performance is achieved by the introduction of sulfonecross-linking that make the bead more resistant to deformation and thuscapable of withstanding higher reactor flow rates. Surprisingly, highcatalyst activity and selectivity for the reaction for bisphenol-A areachieved even at increased cross-linking levels. Without wishing to bebound by theory, it is believed that the resistance to deformation andhigher conversion rates result from the unanticipated interaction of thephenol/acetone reaction mixture with the sulfone cross-linkedpolysulfonated resin catalyst structure. The ability to produce morebisphenol product in a given time, which is afforded by a higherreaction rate and flow rate in such processes, is an advantage that isreadily apparent to those skilled in the art.

EXPERIMENTAL EXAMPLES

[0028] In the following examples, all reagents used are of goodcommercial quality, unless otherwise indicated, and all percentages andratios given herein are by weight unless otherwise indicated.

EXAMPLE 1

[0029] Example illustrates the typical preparation of the jetted PS/DVBcopolymer beads useful in making the sulfone-bridged strongly acidic,cation exchange resin beads of the present invention.

[0030] An aqueous suspending medium was prepared containing 0.55% ofAcrysol A-3 polyacrylic acid dispersant, 0.2% sodium hydroxide, 0.39%boric acid, 0.04% gelatin and having a pH of between 8.5 and 8.7. Amonomer solution was prepared containing 3.6% commercial divinyl benzene(containing 55% pure divinyl benzene and 45% ethyl vinyl benzene), 95.8%styrene 0.3% benzoyl peroxide and 0.3% bis(4-t-butylcyclohexyl)peroxydicarbonate. The monomer mixture was jetted through vibrating jettingorifices 450 μm in diameter, at a rate of 145 kg/hr, into a stream ofthe suspending medium moving at a rate of 386 liter/hr. This dispersionwas conveyed by the flow of suspending medium to a gelling column heldat 63° C. The flow produced a residence time of 3.5 hours in the gellingcolumn, and the conversion of monomer to copolymer during this time was25%. The copolymer was separated from the aqueous phase, which wasrecycled. The copolymer was then held in a finishing kettle for 4 hoursa 65° C., then transferred to a final finishing kettle and held at 80°C. for 1.5 hours, heated to 92° C, and held at that temperature for 1hour. The finished 2.0% divinyl benzene cross-linked polystyrenecopolymer was washed with water and air dried.

EXAMPLE 2

[0031] Example 2 used the process of example 1 to produce a 3.5% divinylbenzene cross-linked copolymer.

EXAMPLE 3

[0032] Example 3 used the process of example 1 to produce a 4.5% divinylbenzene cross-linked copolymer.

EXAMPLE 4

[0033] Catalyst A

[0034] In a one liter round bottom flask containing 75 g of copolymerfrom Example 1 was charged 1,000 g of 96% sulfuric acid and 50 g ofethylene dichloride (EDC). This mixture was heated to 125 C over 1 hourand held at that temperature for 2 hours to remove the EDC and thencooled to 110 C. The sulfonated resin was hydrated at a temperaturebetween 110 C and 60 C by consecutive additions of diluted acid andremoval of the resulting diluted acid until less than 5% acid remained.The catalyst was washed with 2×500 ml of DI water and packed out. Theproperties of catalyst A are presented in Table 1.

EXAMPLE 5

[0035] Catalyst B

[0036] In a one liter round bottom flask containing 75 g of copolymerfrom Example 1 was charged 1,200 g of 102.5% sulfuric acid. This mixturewas heated to 120 C over 1 hour and held at that temperature for 2 hoursand then cooled to 110 C. The sulfonated resin was hydrated at atemperature between 110 C and 60 C by consecutive additions of dilutedacid and removal of the resulting diluted acid until less than 5% acidremained. The catalyst was washed with 2×500 ml of DI water and packedout. The properties of catalyst B are presented in table 1.

EXAMPLE 6

[0037] Catalyst C

[0038] In a one liter round bottom flask containing 75 g of copolymerfrom Example 1 was charged 1000 g of 20% oleum (104.5% sulfuric acid) .This mixture was heated to 120 C over one hour, held at that temperaturefor 2 hours and then cooled to 120 C The sulfonated resin was hydratedat a temperature between 110 C and 60 C by consecutive additions ofdiluted acid and removal of the resulting diluted acid until less than5% acid remained. The catalyst was washed with 2×500 ml of DI water andpacked out. The properties of catalyst C are presented in Table 1.

EXAMPLE 7

[0039] Catalyst D

[0040] In a one liter round bottom flask containing 100 g of copolymerfrom Example 2 was charged 900 g of 96% sulfuric acid and 40 g ofethylene dichloride (EDC). This mixture was heated to 125 C over 1 hourand held at that temperature for 2 hours to remove the EDC and thencooled to 110 C. The sulfonated resin was hydrated at a temperaturebetween 110 C and 60 C by consecutive additions of diluted acid andremoval of the resulting diluted acid until less than 5% acid remained.The catalyst was washed with 2×500 ml of DI water and packed out. Theproperties of catalyst D are presented in table 1.

EXAMPLE 8

[0041] Catalyst E

[0042] In a one liter round bottom flask containing 100 g of copolymerfrom Example 2 was charged 850 g of 20% oleum (104.5% sulfuric acid) .This mixture was heated to 120 C, held at that temperature for 2 hoursand then cooled to 120 C. The sulfonated resin was hydrated at atemperature between 110 C and 60 C by consecutive additions of dilutedacid and removal of the resulting diluted acid until less than 5% acidremained. The catalyst was washed with 2×500 ml of DI water and packedout. The properties of catalyst E are presented in table 1.

EXAMPLE 9

[0043] Catalyst F

[0044] In a one liter round bottom flask containing 100 g of copolymerfrom Example 3 was charged 800 g of 96% sulfuric acid and 40 g ofethylene dichloride (EDC). This mixture was heated to 125 C over 1 hourand held at that temperature for 2 hours to remove the EDC and thencooled to 110 C. The sulfonated resin was hydrated at a temperaturebetween 110 C and 60 C by consecutive additions of diluted acid andremoval of the resulting diluted acid until less than 5% acid remained.The catalyst was washed with 2×500 ml of DI water and packed out. Theproperties of catalyst F are presented in Table 1. TABLE 1 CatalystProperties Catalyst A B C D E F % DVB 2% 2% 2% 3.5% 3.5% 4.5% MHC 82.4%77% 74.2% 71.5% 66.2% 65% Wt. Cap. 5.08 mmol/g 5.67 mmol/g 5.63 mmol/g5.09 mmol/g 5.53 mmol/g 5.09 mmol/g Vol. Cap. 0.63 mmol/ml 1.09 mmol/ml0.94 mmol/ml 1.11 mmol/ml 1.44 mmol/ml 1.32 mmol/ml % Sulfur 16.25 18.8619.47 16.28 19.02 16.2 mmol  0  3.7  7.5  0 10.8  0 sulfone bridginggroups

EXAMPLE 10

[0045] This example illustrates the catalytic activity of the stronglyacidic cation exchange resins of the present invention in catalyzing thecondensation of phenol and acetone.

[0046] The catalytic activity of the ion exchange resin catalysts forBPA synthesis was determined using a CSTR reactor with a reactionmixture containing a phenol to acetone molar ratio of 10:1 and atemperature of 70 C. Promoted catalysts were prepared by neutralizing17% of the acidic sites with aminethanethiol promoter. Composition ofthe reaction mixture was determined by HPLC using a 250×4 mm columnfilled with Nucleosil C18 and 66% volume methanol in water as the mobilephase. The flow rate was 0.6 ml/minute with photometric detection at thewavelength 290 nm. Acetone conversion was computed from the determinedphenol/BPA ratio and the known phenol/acetone ratio in the startingreaction mixture. The initial reaction rates for both promoted and nonpromoted catalysts are presented in Table 2.

EXAMPLE 11

[0047] This example illustrates the resistance of deformation of thestrongly acidic cation exchange resins of the present invention under aforce of up to 200 gram per bead. The compression modulus of thecatalyst was measured in phenol swollen state using a Chatillioninstrument with the compression modulus being the slope of the linemeasuring the initial deformation of the bead up to a force of 200grams/bead. The higher the compression modulus value, the more resistantthe material is deformation under an applied force. The results arepresented in Table 2. TABLE 2 Catalyst A B C D E F % DVB 2% 2% 2% 3.5%3.5% 4.5% sulfone  0 0.22 mmol/g 0.45 mmol/g  0 0.41 mmol/g  0 bridginggroups Compression 472 743 1992 700 3265 740 modulus Unpromoted  6.4mmol/g hr  6.7 mmol/g hr  6.1 mmol/g hr  6.6 mmol/g hr  7.9 mmol/g hr 2.6 mmol/g hr initial reaction rate Promoted 47.4 mmol/g hr 64.2 mmol/ghr 34.1 mmol/g hr 20.4 mmol/g hr 22.6 mmol/g hr 18.1 mmol/g hr initialreaction rate

I claim:
 1. A sulfonated, cross-linked ion exchange resin catalystcomprising monomer units of (a) from 0.1 to 10 percent by weight of oneor more polyvinylaromatic monomers and (b) from 90 to 99.9 percent byweight of one or more monounsaturated vinylaromatic monomers; whereinthe catalyst contains 0.1 to 1.0 millimole sulfone groups per gram drycatalyst, and has an acid capacity of 4.0 to 6.0 millimole sulfonic acidgroups per gram dry catalyst.
 2. The cross-linked ion exchange resincatalyst of claim 1, wherein the catalyst is in the form of sphericalbeads and is capable of catalyzing the formation of at least onebisphenol upon contacting phenols and aldehydes or ketones.
 3. Thecross-linked ion exchange resin catalyst of claim 2, wherein thecatalyst resin beads are prepared from a jetted, suspension polymerizedpolystyrene/divinylbenzene copolymer having from 0.1 to 1.0 millimole ofsulfone groups per gram of dry catalyst.
 4. A catalyst for producing atleast one bisphenol, which comprises contacting phenols and aldehydes orketones with a sulfonated, cross-linked ion exchange resinfunctionalized with strongly acid cation-exchange groups.
 5. Thecatalyst according to claim 4, wherein at least one bisphenol isbisphenol-A.
 6. The catalyst according to claim 4, wherein the phenolsand aldehydes or ketones are from about 1% to about 40% by weight, basedon the total weight of the phenols and aldehydes or ketones.
 7. Thecatalyst according to claim 4, wherein the ion exchange resin is in theform of spherical beads prepared from a jetted, suspension polymerizedpolystyrene/divinylbenzene copolymer having from 0.1 to 1.0 millimole ofsulfone groups per gram of dry catalyst.
 8. The catalyst according toclaim 4, wherein 1 to 35 mol % of the sulfonic acid groups contain anionically attached thiol promoter.
 9. A process for catalyzingcondensation reactions between phenols and aldehydes or ketonesproducing one or more bisphenols, which comprises contacting the phenolsand aldehydes or ketones with a sulfonated, cross-linked ion exchangeresin finctionalized with strongly acid cation-exchange groups.
 10. Theprocess according to claim 9, wherein at least one bisphenol isbisphenol-A.
 11. The process according to claim 9, wherein the phenolsand aldehydes or ketones are from about 1% to about 40% by weight, basedon the total weight of the phenols and aldehydes or ketones.
 12. Theprocess according to claim 9, wherein the ion exchange resin is in theform of spherical beads prepared from a jetted, suspension polymerizedpolystyrene divinyl benzene copolymer having from 0.1 to 1.0 millimoleof sulfone groups per gram of dry catalyst.
 13. The process of claim 9,wherein the phenol and acetone are present in a ratio of from about 20:1to about 2:1.
 14. The process of claim 9, wherein the temperature atwhich the reactants contact the beads is from about 40° C. to about 100°C.
 15. The process of claim 9, wherein 1 to 35 mol % of the sulfonicacid groups contain an ionically attached thiol promoter.
 16. A processfor preparing bisphenol-A from phenol and acetone in a fixed bed reactorcomprising a sulfonated, cross-linked ion exchange resin finctionalizedwith strongly acid cation-exchange groups.
 17. The process according toclaim 16, wherein the ion exchange resin is in the form of sphericalbeads prepared from a jetted, suspension polymerized polystyrene divinylbenzene copolymer having from 0.1 to 1.0 millimole of sulfone groups pergram of dry catalyst.
 18. The process of claim 16, wherein the phenoland acetone are present in a ratio of from about 20:1 to about 2:1. 19.The process of claim 16, wherein 1 to 35 mol % of the sulfonic acidgroups contain an ionically attached thiol promoter.
 20. A process forpreparing a sulfonated cross-linked ion exchange polymer of claim 1,comprising the steps of contacting a polystyrene polymer crosslinkedwith 1-8% divinylbenzene with sulfuric acid of concentration between 101and 106%, an acid to copolymer ratio of 6:1 to 20:1, at a temperaturebetween 80 and 140 C, for 1 to 10 hours.